EPA-450/3-73-006-h
July 1975
ENGINEERING
AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE
PETROCHEMICAL INDUSTRY
VOLUME 8: VINYL CHLORIDE
MANUFACTURE
BY THE BALANCED PROCESS
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
-------
TECHNICAL REPORT DATA
{Please read Inuructions on the reverse before completing}
T. REPORT NO.
EPA-450/3-73-006-h
2.
3. RECIPIENT'S ACCESSIO^NO.
4. TITLE AND SUBTITLE
Engineering and Cost Study of Air Pollution Control
for the Petrochemical Industry, Volume 8: Vinyl
Chloride Manufacture by the Balanced Process
5. REPORT DATE
July 1975
6. PERFORMING ORGANIZATION CODE
7. AUTHOFIS)
R. G. Bellamy, W. A. Schwartz
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Houdry Division/Air Products and Chemicals, Inc.
P. 0. Box 427
Marcus Hook, Pennsylvania 19061
ID. PROGRAM LLEMENT NO.
11. CONTRACT/GRANT NO.
68-02-0255
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Air Quality Planning & Standards
Industrial Studies Branch
Research Triangle Park, N.C. 27711
13. TYPE OF RFPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
16. SUPPLEMENTARY NOTES
16. ABSTRACT
This document is one of a series prepared for the Environmental Protection
Agency (EPA) to assist it in determining those petrochemical processes for which
standards should be promulgated. A total of nine petrochemicals produced by
twelve distinctly different processes has been selected for this type of in-depth
study. Ten volumes, entitled Engineering and Cost Study of Air Pollution Control
for the Petrochemical Industry (EPA-45Q/3-73-006a through j) have been prepared.
A combination of expert knowledge and an industry survey was used to select
these processes. The industry survey has been published separately in a series of
four volumes entitled Survey Reports on Atmospheric Emissions from the Petrochemical
Industry (EPA-450/3-73-005a, t, c, and d).
This volume covers the manufacture of vinyl chloride by the balanced process.
Included is a process and industry description, an engineering description of
available emission control systems and the cost of these systems.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b. IDENTIFIERS/OPEN ENDEDTERMS
c. COSATI Field/Group
Air Pollution
Petrochemical Industry
7A
Vinyl Chloride
Ethylene Dichloride
7B
Hydrocarbons
7C
Chiorohydrocarbons
11G
13B
13H
18. DISTRIBUTION ST A I t ME N T
19. SECURITY CLASS /This Report j
21. NO. OF FAGES
Unclassified
20. SECURITY CLASS /This page)
1
Unclassified
EPA Form 2220-1 (9-73)
-------
EPA-450/3-73-006-b
ENGINEERING
AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE
PETROCHEMICAL INDUSTRY
VOLUME 8: VINYL CHLORIDE
MANUFACTURE
BY THE BALANCED PROCESS
by
R.G. Bellamy and W.A. Schwartz
Houdry Division
Air Products and Chemicals, Inc.
P. O. Box 427
Marcus Hook, Pennsylvania 19061
Contract No. 68 02~0255
EPA Project Officer: Leslie Evans
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
July 1975
-------
This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers. Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - as supplies permit - from the
Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711; or, for a
fee, from the National Technical Information Service, 5285 Port Royal
Road, Springfield, Virginia 22161.
This report was furnished to the Environmental Protection Agency by
Houdry Division of Air Products and Chemicals, Inc., Marcus Hook,
Pennsylvania 19061, in fulfillment of ConLract No. 68-02-0255, The
contents of this report are reproduced herein as received from Houdry
Division of Air Products and Cheniicals, Inc. The opinions, findings,
and conclusions expressed arc those of the author and not necessarily
those of the Environmental Protection Agency. Mention of company
or product names is not to be considered as an endorsement by the
Environmental Protection Agency.
Publication No. EPA-4'>0/3-73-006-h
ii
-------
In-Depth Study
of
VINYL CHLORIDE MONOMER PRODUCTION
Contract No. 68-02-0255
Prepared For
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Prepared By
Houdry Division
Air Products and Chemicals, Inc.
P„ 0„ Box 4 27
Marcus Kook, Pennsylvania 19061
Houdry
Division
A
-------
PETROCHEMICAL AIR POLLUTION STUDY
INTRODUCTION TO SERIES
This document is one of a series prepared for the Environmental
Protection Agency (EPA) tc assist it in determining those
petrochemical processes for which standards should be promul-
gated. A total of nine petrochemicals produced by 12 distinctly
different processes has been selected for this type of in-depth
study. These processes are considered to be ones which might
warrant standards as a result of their impact on air quality.
Ten volumes, entitled Engineering and Cost Study of Air Pollution
Control for the Petrochemical Industry (EPA-450/3-73-0Q6a
through j) have been prepared.
A combination of expert knowledge and an industry survey was
used to select these processes. The industry survey has been
published separately in a series of four volumes entitled
Survey Reports on Atmospheric Emissions from the Petrochemical
Industry (EPA-450/3-73-005a, b# c and d).
The ten volumes of this series report on carbon black,
acrylonitrile, ethylene dichloride, phthalic anhydride (two
processes in a single volume), formaldehyde (two processes in
two volumes), ethylene oxide (two processes in a single
volume),high density polyethylene, polyvinyl chloride and
vinyl chloride monomer.
-------
ACKNOWLEDGEMENTS
The study reported in this volume, by its nature, relied
on the fullest cooperation of the companies engaged jr. the
production of vinyl chloride monomer. This was given at a
particularly difficult time as all the companies were in
the midst of an all out effort to reduce all vinyl chloride
monomer emissions to a minimum. Without their information
this report could not have been written. We, therefore,
list the participating companies to acknowledge their
cooperation and assistance.
Allied Chemical Corporation
American Chemical Corporation*
Continental Oil Company
Monochem, Inc.
FPG Industries, Inc.
Shell Chemical Company
Tenneco Chemical, Inc.
*Subsidiary of Stauffer Chemical Company
-------
TABLE OF CONTENTS
Section
Title
;age Number
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
Introduction
Commercial Processes
Plant Emissions
National Emission Inventory
Industry Growth Projection
Emission Control Devices
Model Plant
Research and Development Goals
VCM-1
VCM-2
VCM-12
VCM-26
VCM-27
VCM-29
vcm-46
VCM-53
re
Title
Page Number
VC-1
VC-2
VC-3
VC-4
vc-5
VC-6
Acetylene Process for Vinyl Chloride
Production
Balanced Chlorination Process for
Producing Dichloroethane
Lichloroethane Cracking Process for
Vinyl Chloride Production
Transcat Process for Vinyl Chloride
Production
Distribution Curve for VCM Emissions
Vinyl Chloride Monomer Yearly
Production
VCM-3
VCM-5
VCM-7
VCM-10
VCM-25
VCM-28
Table
Title
Page Number
VC-1
VC-2
VC-3
Vinyl Chloride Monomer Plant
Net Material Balance
Summary of U.S. Vinyl Chloride Plants
National Emission Inventory for VCM
Manufacture
VCM-9
VCK-11
VCM-13
thru 20
-------
TABLE OF CONTENTS
(CONTINUED)
Table Title
VC—'l- Typical Oxychlorination Vent Gas
Composition
VC-5 Statistical Analysis of VCM Emissions
for 8 VCM Plants in U.S.
VC-6 Thermal Incinerator and Scrubber System
for Oxychlorination Process Vent
VC-7 Direct Fired Boiler Plus Scrubber
Emission Control System for
Oxychlorination Process Vent
VC-8 Thermal Incinerator Plus Steam
Generation and Scrubber System
for Oxychlorination Process vent
VC-9 VCM Emissions from VCM Plants
VC-10 Vinyl Chloride Manufacturing Cost for a.
Typical Existing 700 MM Lbs.At. Plant
VC-11 Vinyl Chloride Manufacturing Cost for
700 MM Lbs./Yr. Plants with Control
Devices
VC-12 Pro-Forma Balance Sheet 700 MM Lbs./Yr.
VCM Plant
V /
Page Number
VCM-21
VCM-24
VCM-34
VCM-37
VCM-39
VCM-40
VCM-50
VCM-51
VCM-52
-------
VCM-1
I. Introduction
The production of vinyl chloride monomer (VCM) has become
a big volume business. Some of the older existing plants
are in the 150 to 200 million pounds per year capacity
range. It is believed that virtually all new plants will
be designed to produce in excess of 500 million pounds of
VCM per year. This is because the economics of produc-
tion definitely favor large volume raw material supply and
large equipment. Almost all the VCM produced goes into
the manufacture of polyvinyl chloride (PVC). A very small
amount is used as an intermediate to manufacture methyl
chloroform (CH3°CCl3), a specialty solvent. A small
quantity was previously used in special aerosol sprays
(insecticides, fungicides, etc.) but this use has recently
been banned in the United States. Therefore the growth of
VCM is exactly tied to the growth of PVC. In 197 3 tota]
U.S. production of VCM exceeded 4.7 billion pounds.(2)
Over ninety percent of the vinyl chloride monomer produced
in the United States is obtained by cracking dichloroethane.
An older process using acetylene and hydrogen chloride feed
has been virtually completely replaced by the dichloroethane
route because of the high cost of acetylene. The capacity
of acetylene type plants is about 10-12% but actual production
from them is much less.
In most cases, overall vapor emissions from the cracking
operation are small in quantity. The vapor emissions do
include a small amount of VCM. The problems of VCM air
emissions in these plants are similar to those encountered
in PVC production. However, VCM plants have one big advantage,
they employ a continuous process as opposed to the PVC batch
type processes. This means that VCM emissions from these
plants are considerably less per unit of production.
This report concentrates on VCM emissions, not hydrocarbon
and particulate losses. It also contains information on VCM
losses from ethylene dichloride (EDC) plants using the
oxychlorination process. This latter information was not
included in a previous in-depth study of the oxychlorination
process.(4) Prior to January 1974 it was not known that VCM
was carcinogenic at low concentrations (under 500 PPM). Because
of this, EDC manufacturers had not attempted to analyze or
report the presence of VCM in the oxychlorination vent streams.
The emission losses used in the present report are based on
information obtained prior to September 1974. There has been
much money and effort spent to reduce VCM emission losses from
EDC and VCM manufacture since that time as well as much improve-
ment made in the detection of low concentrations of VCM (under
10 PPM)* VCM emissions have undoubtedly been substantially
reduced since the summer of 197 4.
-------
VCM-2
II. Commercial Processes
Acetylene and hydrogen chloride are used as starting
materials in the oldest commercial process. In this country,
this is a minor process because economics favor ethylene
as a raw hydrocarbon feedstock over acetylene. However,
there are two plants still using this process.
The reaction is as follows:
C2H2 + HC1 > CH2 = CHC1
The reaction is catalyzed by mercuric chloride (10$) on an
activated carbon base and is carried out at 195 to 285°F.
The reactants are fed at a 1:1 mol ratio and the reaction
goes to approximately 98 to 99$ completion. The reaction
is very exothermic and temperature must be controlled care-
fully. The reactor pressure is low ( 2.5 a tin.) for safety
reasons. Acetylene becomes increasingly hazardous
(explosively) at elevated pressures. If acetylene could be
produced nearly as cheaply as ethylene (say within a half
a cent.per pound), this process could compete with ethylene
process as there are no major by-products to consider.
However at the current differential of 5 "to 10 cents per
pound, the use of acetylene is too expensive to consider
for any new plants and makes existing plants marginal.
Figure VC-1 shows a simplified flow diagram for the acetylene
process. Plants VC-7 and VC-9 are the only plants surveyed
in this study that use the acetylene process.
In the principal process currently used to produce VCM, dry
dichloroethane (also named ethylene dichloride) is dehydro-
chlorinated to vinyl chloride in a cracking furnace.
The chemical reaction is as follows:
CH2CICH2CI > CK2 = CHCl + H.C1
The dichloroethane for this cracking opers.tion is normally
produced by two commercial processes. One is the direct
chlorination of ethylene with chlorine;
-------
FIGURE VC-I
ACETYLENE PROCESS
FOR
VINYL CHLORIDE PRODUCTION
HCI
HCI
ACETYLENE
MIXER
VCM
LIGHT C2 CHLORINATED
^ COMPOUND
<
0
3C
1
U>
REACTOR
HCI TOWER
VCM TOWER
-C2
HEAVY
CHLORINATED COMPOUND
TO WASTE OR
INCINERATOR
CHLOROCARBONS TOWER
( OPTIONAL)
-------
VCM-4
2 CH2 = CH2+ 2 Cl2 > 2 CH2CICH2CI
It can also be produced "by the oxychlorination of ethylene
with HC1:
2 CH2 = CH2 + O2 + ^ HC1 > 2 CH2C1CH2C1 + 2 H20
In most plants producing VCM from EDC, both of the above
chlorination processes are employed, see Figure VC-2, All
HC1 produced in the EDC pyrolysis is normally used as feed
to the oxychlorination reactors. The production of EDC by
the two chlorination routes is balanced so that there is
no net HC1 production or consumption„ On this basisr EEC
production is about evenly split between the two processes.
In the direct chlorination section of the EEC based plant,
chlorine and a substantially stoichiometric amount of
ethylene are fed into a reactor under constant temperature
conditions, excesses of either reactant result in raw
material losses. The reaction usually takes place in the
liquid phase. The exothermic heat of reaction, 52 kcal/
mole, is removed by jacketed walls, internal cooling coils
or external heat exchange„(3) Typical reaction conditions
are temperatures of 100-120°F and pressures in the range
of 10-20 PSIG. Overall process yield of ethylene dichloride
from chlorine is generally better than 98 percent if high
purity reactants are used* However, the presence of
impurities in either ethylene or chlorine will reduce the
reaction yield. Usually a liquid and a vapor stream exit
from the reactor. The vapors pass through water cooled
condensers, and in some cases refrigerated exchangers
where some ethylene dichloride is recovered. The vapors
are sent through an absorbing column where dichloride is
recovered and small quantities of hydrogen chloride and
chlorine are removed. The scrubbing liquid is either water
or dilute caustic, depending on the amount of chlorine
that is desired to be removed.
In the oxychlorination section of the plant approximately
stoichiometric proportions of ethylene, anhydrous hydrogen
chloride and air (except one plant which uses pure oxygen)
are fed to a catalytic reactor which operates at low
pressure (20-75 PSIG) and 400 to 600°F.(^) Once through
flow is used since conversion of ethylene is virtually
complete. Because of the high exothermic heat of reaction
(>55 kcal/mole of EDC produced), efficient heat removal
in the reactor is important for adequate temperature control.
For this reason, some processes utilize fluid bed reactors
with internal cooling coils while at least one producer
-------
FIGURE VG-2
BALANCED CHLORINATION PROCESS
FOR
PRODUCING
dichloroethane
TO CRACKING
DICHLOROETHANE
LIGHT
ENDS
UNIT
OXYCHLORINATION
PROCESS VENT
(/> Zj
AIR OR (3
OXYGEN
OXYCHLORINATION
REACTOR
AND QUENCH
AREA
DECANTER
WATER A
HEAVY
ENDS
HCL
(RECYCLED
FROM EDC
CRACKING
SECTION)
DILUTE CAUSTIC
OR
WATER
SPENT
. CAUSTIC
8 )
WASTE WATER
ETHYLENE
DIRECT
CHLORINATION
REACTOR
CAUSTIC
SODA
WASTE WATER
CHLORINE
DICHLOROETHANE
RECYCLED FROM EDC
CRACKING SECTION
(1) Includes solvent secondary recovery of EDC from oxychlorination process vent.
-------
VCM- 6
employs fixed bed multi-tube reactors which resemble heat
exchangers. In this design, catalyst is contained inside
the tubes and a coolant flows through the shell. In both
fluid bed and tubular reactors, most of the heat removed
is recovered as steam.
The reactor effluent is normally cooled by either direct
water quench or indirect heat exchange. After trim cooling
with water and brine condensers, the partially condensed
effluent is sent to a phase separator. Non-condcnsable
gases consisting mainly of nitrogen are vented to the
atmosphere. Before venting, usually these gases arc
contacted with either water or aromatic solvent for removal
of HC1 and recovery of ethylene dichloride. One process
incorporates chlorine addition downstream of the main
oxychlorination reactor in order to convert unrcacted
ethylene to EDC. In addition to reducing ethylene loss
in the vent gas, the direct ch]orination step reduces the
amount of air required for oxychlorinat.ion. Therefore, the
total volume of vent gas and hydrocarbon emissions are
reduced in volume. The total volume of vent gas is even
smaller for the one unit incorporating tonnage oxygen.
The organic liquid product from the reactor effluent phase
separator and the crude FDC produced by direct chlorination
is contacted with aqueous caustic soda to remove traces of
HC1 and sent to product distillation for removal of water
and chlorinated hydrocarbon impurities before the
dichlorethane is sent to the cracking furnace for VCM
production.
In the cracking furnace, the EEC passes through furnace
tubes at 900 to 950°F and 50 PSIG. Dichloroethane conversion
is about 50% and yield to vinyl chloride is 94 to 97 mole
percent based on EDC fresh feed. The hot effluent gases
are then quenched, and partially condensed, by direct
contact with cold dichloroethane in a quench tower, see
Figure VC-3.
Effluent fractionation and product purification are
generally accomplished in three additional towers. However,
each producer of VCM has his own minor modifications in
the fractionation section which typically includes the
following operations. Hydrogen chloride and light chlori-
nated hydrocarbons are rejected overhead in the "HC1" and
"Light Ends" towers. The hydrogen chloride is normally
recovered and recycled to the oxychlorination plant
reactors as previously indicated. Trichloroethane,
and other heavy ends are rejected from the bottoms of the
"VCM tower" by fractionation and the contained dichloro-
ethane is recycled to the cracking furnace. The light and
heavy ends are either further processed or disposed of by
-------
FIGURE VC-3
DICHLOROETHANE CRACKING PROCESS
FOR
VINYL CHLORIDE PRODUCTION
DICHLOROETHANI
TO
STACK
HCI RECYCLED
TO
OXYCHLORINATION
REACTORS
cb
EDC INTERMEDIATE
STORAGE
FUEL
VAPORIZER
EDC RECYCLED
TO
CRUDE EDC
FRACTIONATION
LIGHT
HYDROCARBONS
ETC.
PYROLYSIS QUENCH HCI LT. ENDS
FURNACE TOWER TOWER TOWER
(OPTIONAL)
(
I
jjS)
VCM
PRODUCT
VCM
STORAGE
VCM
TOWER
TRICHLOROETHANE
PERCHLOROETHYLENE
HEAVIES TO
WASTE OR
INCINERATOR
C2 CHLOROCARBONS
TOWER
(OPTIONAL)
J
-------
vcm-8
incineration and other methods,, Dichloroethane from the
bottom of either the "quench" tower or the "vinyl" tower
is cooled and used as effluent quench. Vinyl chloride
monomer is taken overhead in the "VCM tower1, generally
caustic washed, and then sent 1;o the product storage
facilities.
Six of the eight VCM plants surveyed incorporate the
dichloroethane cracking process. A typical material
balance for the balanced process with EDC cracking is shown
in Table VC-1.
A new process that is not used by any commercial plants as
yet, is one that uses ethane and chlorine as the raw feed.
This "Transcat" process is licensed by C-E Lummus and is
reportedly able to handle a variety of feedstocks. It
also has a waste disposal (for chlorinated hydrocarbon
wastes) operation incorporated into the general process.
If the overall economics are as claimed, this may become
an important process in the future. The overall reaction
to convert ethane to VCM is represented by the following:
C2H6 + 1/2 O2 + CI2 » CH2 = CHC1 + HC1 + H2O
The actual reactions are much more complicated and involve
copper salt complexes. A mixture of cuprous and cupric
chlorides are used as the catalyst and potassium chloride
is used also to control and lower the melting point of the
copper salts. Figure VC-4 shows a simplified flow diagram
for the Transcat process.
It is always possible that in the future, more economical
processes will be found, yor instance, if a new process
was found to produce acetylene so that it was nearly
competitive with ethylene, the trend would swing back to
the original acetylene type process for VCM production.
However, at present, the dichloroethane cracking process is
far and away the most predominate method used for making
VCM.
Table VC-2 presents a list of U.S. plants producing VCM.
This table shows plant location and published(5) capacity
figures for these units.
-------
TABLE VC-1
TYPICAL MATERIAL BALANCE FOR VCM
PRODUCTION VIA BALANCED ETHYLENE PROCESS
Stream I.D.
1
2
3
4
5
6
7a
7b
8
9
Hi
112
>
e*>
>
\t-
10
Raw Materials
Intermediates
By-Products
Water Streams
Vent Streams
Product
Components
C2H4
CL2
Air
EDC
HC1
H2O
Lights
Heavies
H2O
Dilute
Caustic
EDC
Direct
EDC
Oxy
Dist
VCM
Carbon Dioxide
0.0003
(4)
0.0116
Carbon Monoxide
(4)
0.0032
N'i trogen
0. 5782
(4)
0. 5779
0.0003
Oxygen
0.1537
(4)
0.0214
Chlorine
0.5871
0.0001
0.0001
Hydrogen Chloride
0.6036
Water
0.0171
0.1438
0.1166
0.0030
0.0413
Caustic Soda
0.0008
Sodium Chloride
0.0014
Ethylene
0.4656
0.0025
Other Hydrocarbons
0.0002
1. 6370
0.0001
EDC
0.0017
0.0012
0.0016
0.0017
0.0045
VCM
(2)
0. 0008
0.0001
0.0012
0.0024(2)
1.0000(3)
Light Chlorocarbons
0.0017
0.0012
0.0003
0.0025
Heavy Chlorocarbons
0.0023
Total, Lbs./Lb. VCM
0.4658
0.5871
0.7493
1.6370
0.6036
0.1438
0.0042
0.0047
0.1180
0.0038
0.0045
0.6609
0.0 07 5
1.0000
Notes:
(1) The amount of EDC in this column represent the EDC necessary for a stoichiometric balance including the amount that is
changed to other products (i.e., heavy chlorocarbons), but does not include any recycle EDC.
(2) VCM fugitive emissions are included in this category in order to make a material balance even though part of the actual
losses occur elsewhere.
(3) Excludes storage and loading losses of VCM. The average of these losses for surveyed plants was 0.0008 lbs./lb. product.
(4) Inerts present in chlorine feed will be emitted in this vent stream.
(5) Miscellaneous intermittent emissions not noted in this material balance, 6uch as sampling,annual vessel openings, miscel-
laneous fugitive emissions, etc. amount to about 0.0001 lbs/lb. product.
-------
FIGURE VC-4
TRANSCAT PROCESS
FOR
VINYL CHLORIDE PRODUCTION
OXIDATION
REACTOR
WASTE
CHLOROCARBONS
BY-PRODUCTS
PYRO LYSIS
FURNACE
\
-AIR
1
J
V
GAS
~
LIFTS
*
~
EFFLUENT
PROCESSING
SECTION
CHLOR/OXY
REACTOR
4
^ETHANE
_C I OR_
HCl
HCl
EFFLUENT
PROCESSING
SECTION
- V,
^ t?
) MOLTEN SALT
1
SEPARATION
SECTION
WASTE CHLOROCARBONS
n2, C02
h2o
jSE* H20
W VINYL CHLORIDE
ss- TRICHLOROETHYLENE
P* PERCHLOROETHYLENE
o
2
-------
VCM-11
TABLE VC-2
SUMMARY OF U.S. VINYL CHLORIDE PLANTS
Published
Capacity,
Company Location MM Lbs./Yr.
Allied Chemical.
Baton Rouge, Louisiana
300
American Chemical
Long Beach, California
17 0
Conoco
Lake Charles, Louisiana
700
Dow Chemical
Freeport, Texas
Plaquemine, Louisiana
Oyster Creek, Texas
180
340
800
Ethyl Corporation
Baton Rouge, Louisiana
Pasadena, Texas
270
150
B. F. Goodrich
Calvert City, Kentucky
1,000
PPG Industries
Lake Charles, Louisiana
Guayanilla, Puerto Rico
300
575
Shell Chemical
Deer Park, Texas
Norco, Louisiana
840
700
Monochem Inc.*
Geismar, Louisiana
300
Tenr.eco*
Pasadena, Texas
225
TOTAL 6,850
* Only plants using acetylene as raw feedstock. All other
plants use dichloroethane.
-------
VCM-12
III. Plant Emissions
Table VC-3 shows individual plant capacity figures and
VCM emission data for eight of the ten manufacturers of
VCM. Emission sources from these plants are as follows:
A. Continuous Air Emissions
One company (VC-2) states that they have no continuous
emission losses other than fugitive emissions and. that
these losses are very low based on material balance.
However, they do not indicate any emissions from the
oxychlorination unit where there are probably some
VCM losses.
All the other companies have continuous losses which
are often fed into control devices along with inter-
mittent streams. The continuous air emissions are as
foJlows:
1. Distillation Columns - Most of the plants have
distillation columns to separate impurities from
the EDC (.Source Areas A & 7a) or from VCM (Source
Area A]_) . The inert gases from these columns (after
refriaeration, scrubbing, etc.) contain some VCM..
Depending on the plant, this vent is either emitted
to the air or is vented to a control device.
2. Flash Drums - Several VCM plants have a flash drum
to separate vinyl chloride from neutralizing
water streams. The VCM vapors are generally fed
to an emission control device (Source Area R).
3. Vent Reactor Vent - One acetylene plant (VC-9) has
a vent reactor which is actually a small reactor
designed to take the gaseous effluent from the main
reactor and react as much as possible of the
remaining reactants to completion (VCM). The vent
from this secondary reactor is sent to the purifi-
cation system where the inerts arc vented to the
atmosphere (Source Area E).
4. Oxychlorination Vent Gas - This stream, which
generally vents from a scrubber or an absorber,
consists of the gross oxychlorination reactor
effluent after quenching and trim cooling for
recovery of EDC. Table VC-4 shows a typical
breakdown of components in this stream, which
represents the primary air emission in the oxy-
chlorination section of the plant (Source Area IT2) -
Catalyst activity, reactor operating conditions and
the specific processing scheme employed have some
influence on the amount of vent gas emissions from
this source. For example, in one process, chlorine
-------
TABLE VC-3
NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE
Plant Code Numbers VC-1
Plant Capacity, Million Lbs.Ar.: 500
Process: Balanced EDC
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCM Emissions
Lbs./Lb. Prod. Tons/Yr,
7a EDC Distillation Column C1)
7a EDC Distillation Column (2)
C Transfer and Loading Losses
D Sampling Losses
Fugitive Losses
ID
VMD-l
VMD-l
VMD-l
VMD-17
.000175
.000354
.000048
.000001
9
Total
,000578
144.5
Notes:
(1) Vent from EDC column in associated direct chlorination unit.
(2) Vent from EDC column in associated oxyhydrochlorination unit.
(3) Flow sampling loops.
(4) No estimate of fugitive emission given - no material balance.
-------
TABLE VC-3
NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE
Plant Code Number: VC-2
Plant Capacity, Million Lbs./Yr.: 300
Process: Pyrolysis of EDC
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCM Emissions
Lbs./Lb. Prod
Tons/Yr,
B Released From Neutralizer Water
C Dock & RR Tank Car Loading Loss
D Sampling (3)
F Neutralizers and Filters (4)
F&G Dryers and Process Vessels (4)
Fugitive (5)
Total
VMD-1
VMD-2
VMD-17
VMD-1
VMD-1
.000015
.001214
.000001
o000002
.000032
9
0OO1264
189.6
Motes
f 31
4
5
Vent from flash pot releasing.
All major VCM emission streams returned to absorber to be recycled in EDC streams,
This loss will drop to approximately <,000174 by mid 1975 when dock loading losses
are connected to system.
Sampling losses minimized by sampling loop.
Intermittent emissions.
No estimate or material balance given.
-------
TABIE VC-3
NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE
Plant Code Number: vc-3
Plant Capacity, Million Lbs./Yr.: 840
Process: Balanced EDC
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCM Emissions
Lbs./Lb. Prod.
Tons/yr.
A
C
D
Scrubber Vent Stack -
Collects From 8 Areas
Loading Arms and Loading Areas
Flare
Sampling
Fugitive (1)
None
VMD-1
VMD-3
(2)
002355
000048
000023
000052
Total
002478
1040.7
Notes:
(1) Calculated by analogy from emission factors taken from "Control Techniques for Hydrocarbon and
Organic Solvent Emissions From Stationary Sources", Natural Air Pollution Administration,
Publisher Number AP-68, March 1970.
(2) A refrigeration device, VMD-4, is used to condense some of the vapors prior to the flare. No
data are given as to conditions or type of equipment.
-------
TABLE VC-3
NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE
Plant Code Number: VC-4
Plant Capacity, Million Lbs./Yr.:
Process: Balanced EDC
730
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCM Emissions
Lbs./Lb. Prod
Tons/yr,
Main Stack
Loading Losses
Fugitive (1)
VMD-1
VMD-4 (2)
.001368
.001929
9
Total
.003297
1203.4
Notes:
(1) No estimate given or material balance made.
(2) Some type of condensing system is noted but no information is given of conditions
or type of equipment.
-------
TABIJE VC-3
NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE
Plant Code Number: vc-6
Plant Capacity, Million Lbs./Yr.: 320
Process: Pyrolysis of EDC
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCM Emissions
Lbs./Lb. Prod,
Tons/Yr,
A
C
D
G
Light Column Vent
Tank Car Loading
Sampling
Cleaning, Inspections, Etc. of Vessel
Fugitive (1)
Total
VMD-1
VMD-17
000040
000486
000001
000088
000615
104.6
(2)
Notes:
(1) No estimate or material balance given. Statement made that fugitive emissions are very low
due to constant monitoring and good housekeeping.
(2) Based on data provided in June 1974 report. Correspondence with the manufacturer subsequent
to the completion of this study indicates total VCM loss may have been as much as ten times
higher than value shown.
-------
TABLE VC-3
NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE
Plant Code Numbers VC-9
Plant Capacity, Million Lbs./Yr.:
Process: Acetylene
275
Source
Area
E
Description
Vent Reactor Vent (1)
Fugitive (2)
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
VCM Emissions
Lbs./Lb. Prod
Tons/yr.
VMD-1 & VMD-4(3) o003561
0OOI515
Total
O005076
698,0
Notes:
(1) A secondary reactor is incorporated in this plant to reduce total VCK emissions, but
it also has a monetary value in reducing losses significantly.
(2) Estimated from material balance.
(3) No details are given other than the vent are cooled to less than 4o°F.
-------
VCM-21
TABLE VC-4
TYPICAL OXYCHLORINATION VENT GAS COMPOSITION
FOR 530 MM LB./YR. ETHYLENE DICHLORIDE PRODUCTION
BY OXYCHLORINATION
(Total EDC Production Required To Produce 700 MM Lb./Yr.
Of VCM By Balanced Ethylene Process)
Normal Range In Average Flow Rate
Component Composition, Mol.# MPH Lbs./Hr.
Carbon Dioxide
0.8
-
3-5
36.3
1,598
Carbon Monoxide
0.6
-
1.3
15.7
441
Nitrogen
82
-
95
1,881.5
52,706
Oxygen
0.5
-
7.5
92.6
2,962
Methane
0
-
5.0 (c)
8.1
130
Ethylene
0.2
-
0.8
11.4
318
Ethane
0
-
3.8 (d)
14.5
435
Ethylene Dichloride
0.07
-
0.75
4.6
454
Ethyl Chloride
0
-
0.75
6.0
386
Vinyl Chloride
0
-
O.25
1.6
101
Aromatic Solvent (b)
0.
-
0.1
0.7
71
2,073.0
59,602
(a) Downstream of water or caustic scrubber facilities. Prior
to scrubbing operations, stream normally contains about
65 lbs./hr. HC1«
(b) Only present if aromatic solvent is used for product recovery.
(Plant VC-6).
(c) Only present if ethylene and HC1 feed to reactors contains
methane.
(d) Primarily represents saturate impurity in ethylene feed.
(e) Based on data provided by Plant VC-8, may include some losses
from other sources vented through oxychlorination vent stack.
-------
VCM-2 2
is added downstream of the main oxychlorination
reactor in order to convert unreacted ethylene to
EDC. By using chlorine for clcan-up, it is not
essential to obtain maximum conversion in the
oxychlorination reactors. This permits a reduction
.in the amount of excess air employed and also results
in a significant reduction in hydrocarbon emissions.
According to the survey data, hydrocarbon emissions
in the vent gas stream arc about half as much as those
indicated for plants using several other air cxychlori-
natcd processes. In the plants that have chlorine
addition (VC-3, VC-4 and VC-E), the process vent cas
is sent to a water or dilute caustic scrubber for
removal of HC1 (up to 0.0003 T/T VCM) and unreacted
chlorine (about 0.0002 T/T VCM) before this stream
is emitted to the atmosphere.
In some of the other air oxychlorination plants
(VC-6), an absorber-stripper system is used to recover
additional chlorinated hydrocarbons Prom the oxychlori-
nation process vent gas; see Figure VC-2. In these
units, a small amount of absorption oil (aromatic
solvent) is lost in the atmospheric vent (C.Q009 T/T VCK)
However, total hydrocarbon emissions arc similar to the
chlorine addition plants (0.012 T/T VCM).
The oxychlorination vent gas emissions shown in
Table VC-4 approximate a weighted average (based on
EDC capacity) of emissions from all surveyed air
oxychlorination plants. Since about 65% of the air
oxychlorination EDC is produced in plants that
incorporate absorber-stripper or chlorine recovery
systems, the emissions shown in these tables do not
truly represent actual values obtained in any specific
plant. In other words, units with chlorine addition
or lean oil absorption systems would tend tc have lower
hydrocarbon losses than shown for the "typical unit".
Whereas, plants with minimum clean-up facilities would
have a somewhat higher level of hydrocarbon emissions.
In the one U.S. oxychlorination plant usino tonnage
oxygen in place of air (VC-2), total vent gas emissions
are greatly reduced. However, hydrocarbon emissions
for this unit arc similar to those shown in Table VC-4.
Direct Chlorination Process Vent - This is the major
source of air emissions from the direct chlorination
of ethylene. The stream consists of the inerts contained
in the reactor effluent (approximately 0.018 lbs./lb. of
VCM) plus ethylene (0.C025 lbs./lb. of VCM), ethylene
dichloride (0.0016 lbs./lb. of VCM) and small amounts
of vinyl chloride.
-------
VCM-2 3
B. Intermittent Air Emissions
1. Loading Areas - The largest intermittent emissions
are from the loading areas. They can be significant
if VCM is used for purging oxygen from barges and/or
tank cars when this transport equipment is initially
placed in service (Source Area C).
2. Storage Vents - Losses from storage of VCM are very
low as VCM tanks are pressurized and vents are
compressed and recycled (Source Area C).
3. Safety and Relief Valves - This is a small emission
and most plants use rupture discs in front of safety
valves to minimize leakage.
4. Sampling - This emission is low now because all plants
are taking precautions against indiscriminant
emissions to protect the Sampler (Source Area D).
5. Filters, Pumps, Etc. - These are mainly fugitive emis-
sions that can vary markedly depending upon condition
of equipment. Most companies are monitoring continuously
and catch such emissions early (Source Area F).
6. Vessel Openings - Most all equipment is inspected
annually and this means opening the equipment- Most
companies steam out all vessels and emissions are
driven to normal venting areas before vessel is opened
(Source Area G) .
C. Fugitive Emissions
Fugitive emissions are very low and most are calculated
from a material balance. They range from 2 to 50 lbs.
per hour. (0.00004 to 0.00150 lbs. VCM/lb. product.)
D. Liquid and Solid Wastes
About 0.0001 T/T VCM of catalyst particles are removed
from reject water settling ponds in plants that employ
fluidized bed oxychlorination reactors. There are no
other solid wastes resulting from VCM production. Liquid
wastes are light ends, heavy ends, and water. The light
ends are returned to the system for recycle. The heavy
ends (liquid chlorinated hydrocarbons) are separated into
saleable products, i.e., trichloroethane, trichloroethylene,
etc., while the heavier products are generally incinerated.
The waste water is generally warmed to allow the VCM vapors
to escape to some emission control device (normally a
flare or incinerator but sometimes just a high stack).
Table VC-5 and Figure VC-5 show the distribution of reported
total VCM emissions in the various VCM plants.
-------
TABLE VC-5
STATISTICAL ANALYSIS OF VCM EMISSIONS
FOR 8 VCM PLANTS IN U.S.
Code
No.
VC-1
VC-2
VC-3
VC-4
VC-6
VC-1
VC-8
VC-9
Total VCM
Emission
.000578
.001264
.002478
.003297
.000615
.000396
.001484
.005076
Rank
No.
2
4
6
7
3
1
5
8
Rank
No.
1
2
3
4
5
6
7
8
Emission
.000396
.000578
.000615
.001264
.001484
.002478
. 003297
.005076
.015188
1.56816 X 10
-7
-7
-6
-6
3.34084 X 10
3.78225 X 10
1.597696 X 10
2.202256 X 10
6.140484 X 10
1.08702 X 10
2.576577 X 10
Percentile
11,
22.
33.
44.
55.
66.
77.8
88.9
<
0
3
1
N)
.U
4.7445546 X 10
-5
Mean = .00190
Variance = .00000266
Standard Deviation = .00163
-------
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99.99
99.9 99
1 C.5 0.2 0.1 0.05
0.01
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STKN
ENrAGE
:umu DA
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<
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s
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ro
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99.3 99.3
99.99
-------
VCM-2 6
IV. National Emission Inventory
Based on the emissions reported in Table VC-3, the total
VCM air emission from the surveyed plants as of September
1974 (representing about 3.5 billion lbs./yr. VCM capacity)
are approximately as follows:
PROCESS
Balanced Ethylene With VCM,
Pyrolysis of EDC MM Lbs/Yr
VCM Emissions
T/T of VCM Tons/Yr
VC-1
VC-3
VC-4
VC-8
Total
Wt. Average
Pyrolysis of EDC
VC-2
VC-6
Total
Wt. Average
Acetylene
VC-7
VC-9
Total
Wt. Average
500
84 0
730
100
2,170
30 0
34 0
640
300
2 75
575
.000578
. 002478
.003297
.001484
.002270
001264
000615
000916
000396
005076
002634
144.5
1.040.7
1,203.4
74 . 2
2.462.8
189. 6
104 . 6
293.2
59.4
698 . 0
757.4
Total
Wt. Average
3,385
002076
3,513.4
Based on an estimated 5.0 billion lbs./yr. VCM production
rate in the United States during 1974, the total VCM emissions
from VCM production is estimated to be approximately 5,200
tons/yr.
VCM emissions are fairly uniform throughout the year as
production of most plants is at or near (sometimes above)
rated capacity all year and neither ambient temperatures
nor cooling water temperatures are important factors in
controlling VCM emissions.
-------
VC.M-27
V. Industry Growth Projection
The growth of vinyl chloride is directly related
to the growth of polyvinyl chloride as there is no
ether significant use for vinyl chloride. The old
acetylene process for VCM production is gradually
disappearing. Currently most plants use dichloro-
ethane cracking. The latest commercial process
starts with ethane and should grow significantly
if the economics prove to be as good as predicted.
In the past, the overall growth of VCM has been the
same as PVC and should follow the same growth curve
in the future. Several factors that are of very
recent origin may cause a temporary slowdown
(possibly a slight reversal). One is the relating
of angiosarcoma of the liver with VCM emissions.
This has stopped at least temporarily the possible
use of PVC for liquor bottles and possibly all food
uses. Another factor is the "energy crisis" which
could limit the expansion of producing plants. A
third factor is the current (1974-1975) slowdown
of the building industry which uses about half of
the PVC produced nationally.
Figure VC-6 indicates the growth rate from 1962 to
1974 (11.89;) and predicts a future growth to 1985
(4.9$). The lower projected growth rate in the next
decade is a result of an anticipated gradual slowdown
in demand plus other factors noted above.
-------
SEM| LOGAR[THMIC 359-51
Ir^i
-------
VCM-2 9
Emission Control Devices
Any device used to reduce VCM emissions significantly and
is not used for any other reasons (i.e., economic) is
considered an Emission Control Device. In other words,
the device cannot be profitable or it would be a necessary
adjunct to the process.
In VCM manufacture, emission control devices rather than
control procedures are of primary .importance in reducing VCM
losses to the atmosphere. This is because VCM manufacture
involves a continuous process in which VCM emissions are
normally very low (about one-tenth that found in PVC
manufacture) and cannot be changed markedly, if at all, by
changes in process operating conditions or changes in
operating procedural methods. In addition to emission contro
devices, "good housekeeping" and proper equipment maintenance
are important in minimizing VCM emissions.
Listed below are control devices for reducing VCM emissions.
A. Distillation Vents (Source Areas A, A]_ , and 7a)
VMD-1 - Stacks
Many of the plants have vent stacks to the atmosphere
of varying diameters and heights. Most of the stacks
now carrying any significant amount of VCM emissions
are to be replaced by a more positive control device.
The costs of stacks vary widely depending on height,
diameter, location, material, etc.
VMD-2 - Absorbers
The use of EDC as an absorbing media to remove VCM
vapors is very effective. After the VCM is recovered
from EDC in a stripper, the EDC can be fed back to the
pyrolysis unit. In this case, efficient stripping of
VCM from the EDC is not essential. Only one company,
VC-2, reports using such a system and it is the only
plant reporting no continuous emissions other than
fugitive emissions. The cost for this system is the
cost of piping the vents back to the absorber already
in the EDC part of the plant plus any blowers or
exhausters necessary to maintain absorber pressure.
One plant, VC-6, has plans to use this type system with
a calculated 99% VCM recovery efficiency.
VMD-3 - Flares
Three plants, VC-3, VC-6 and VC-7, have vent- streams
containing VCM along with other combustibles directed
to a plant flare. One of these, VC-6, is a pond flare
-------
VCM-3 0
and the pond is lined with limestone to neutralize the
HC1 formed at the flare. This flare was installed (1968)
at a cost of $16,000 and costs about $25,000/year to
maintain with a 20-year life. We have no data on gas
composition to the flare.
VC-3 and VC-7 have typical plant flares and the streams
contain a substantial amount of VCM and other combustibles.
VC-7 contains about 93% combustibles (21% VCM). The flare
is 150' high and 6" in diameter. It burns about 28 0 lbs.
VCM per hour (0.0082 lbs./lb. VCM product). No costs are
given. VC-3 has a 100 ft. stack (1.17 ft. in diameter).
The stream contains about 9 6% VCM and burns about 34 5 lbs.
of VCM per hour (0.0034 lbs./lb. VCM product). Fist.imated
current cost with necessary piping, knockout pot and
refrigeration condenser would be about $200,000. No
operating costs were given. Both plants assume that the
VCM is completely consumed.
If for any reason these flares go "out" a high emission
rate would result.
VMD-4 - Refrigeration
It is possible to reduce VCM emissions by compressing
the fractionation vent streams (70 PSIG) and chill the
stream (40°F) to condense out most of the VCM and vent
the inerts. Such a system for processing the combined
distillation vent from a typical 700 MM lbs./yr. plant
(see Table VC-1) would cost about $200,000 installed.
Assuming the combined feed streams contain 230 lbs./hr.
VCM (45 vol.% of stream) about 200 lbs./hr. of VCM
(0.0025 lbs./lb. of VCM product) would be recovered.
The resulting vent would contain about 0.00038 lbs. of
VCM/lb. of VCM product. Electric power consumption for
the facility would be 4 0 KWB'/hr. plus 4 0 GPM cooling water.
VMD-5 - Carbon Adsorption
No plant has mentioned the possibility of using carbon
adsorption but it may be a feasible system albeit one
requiring considerable development both technically and
economically. In a low volume, high percentage VCM
content system it would be very effective and fairly
economic. In dilute (<5% VCM) systems it becomes
increasingly costly and less feasible technically. Rased
on processing the combined distillation vent derived from
the typical material balance (Table VC-1) we can estimate
the size of an appropriate system. Several assumptions
must be made as follows:
1) Streams cooled to 8 5°F to reduce F,DC content
and improve adsorption.
-------
VCM-31
2) EDC is absorbed by charcoal as easily as
VCM.
3) No poisoning contaminants.
The cooled stream would contain approximately 72.5!$
VCM, 15$ KDC and the balance inerts. Under these
conditions, using a selected activated carbonv6) 0f an
apparent density of 31 lbs./cu. ft., approximately 1000
cu. ft. of activated carbon would adsorb 99-9+$ the
VCM and EDC from the vent streams in a 24-hour on-stream
cycle. A second bed of the same size would be required
to provide continuous processing. The equipment to
handle this adsorption would cost about $200,000 and the
double charge of activated carbon (62,000 lbs.) about
$80,000.
Utility costs would be high as steam (1000 lbs./hr.) or
hot nitrogen (12,000 cu. ft. at 250o-30C°F') would be
required to regenerate the activated carbon beds. The
life of this equipment should be over 15 years and the
life of the activated carbon should be 6 to 12 months
assuming no positive poisoning ingredient in the vent
streams. If there is a poisoning effect or substantial
amounts of inerts present, total cost would be much higher.
VMD-6 - Waste Heat Boilers
One company, VC-8, has a waste heat boiler that burns
a number of hydrocarbons and chlorocarbons including
some VCM. The waste heat boiler is preceded by two
parallel caustic scrubbers for removing HC1 and CI2 from
the vraste feed gas. The boiler effluent is scrubbed
with water to remove HC1 before being vented to the
atmosphere.
A test was made of this waste heat boiler system by
the local Air Pollution Control District. A report was
filed in January 2, 1973 giving particulars of the fuel
consumption and steam production rates. The stream
analytical data presented in this report showed the
waste feed gas,during the test,contained less than 1.5$
combustibles. One interesting point indicated by the
analytical data is that the vinyl chloride was not
completely consumed in the combustion chamber but only
98-99$ of the VCM was destroyed. Unfortunately, operating
temperatures and residence time data were not provided.
An economic analysis of this control device was submitted
to the EPA on December 11, 197^ by plant VC-8. According
to this economic study, the waste heat boiler operation
shows a favorable return on investment. The installed
-------
VCM-32
cost for this facility was $150,000 (in 1972) . The
waste heat boiler feed consists of 53 CFM of chlori-
nated waste gases. The heat content of this gas is
reported to be 600-1300 BTU/ft.3, This indicates a
much higher combustible content than was present
during the January 2, 1973 test. Supplemental fuel
requirement is 2.1 MM BTU/hr. and the boiler produces
5OOO lbs./hr. of steam (average rate). In addition
to supplemental fuel, utility costs include $1050/
year for electric power and $500/year for water.
Cost for chemicals is estimated to be $1000/year.
Maintenance charges are estimated at $5,000/year.
Plant VC-1 is installing In 1975* a combination
incinerator, waste heat boiler and scrubbers (to
remove HC1) at an estimated cost of 2-1/2 million
dollars. There is an estimated total annual cost of
slightly over 1/2 million dollars but this is offset
by an expected heat recovery worth approximately a
quarter of a million dollars per year. Only about 20$
of this system is directly attributable to VCM plant
emission but there is no mention of how much is due
to the balanced EDC plant (oxychlorination vent).
The incinerator will operate in excess of l600°F. At
this temperature level, they expect the VCM to be
completely (100$) destroyed,
B. Oxychlorination Vent Gas (Source Area H2)
VMD-7 - Thermal Incinerator and Scrubber System
None of the plants covered in this survey presently
have an incinerator to burn the oxyhydrochlorination
process vent gas. One company (VC-3) has roughly
estimated that the capital cost of incinerating the
oxyhydrochlorination vent scaled to a 700 MM lbs./
year VCM plant would be about $2.5 to 4.25 million
dollars with a total annual charge of 0.55 to 0.95
million dollars. In other words, they estimate it
would increase the cost of VCM about 1/8 cent per
pound to incinerate the vent from the oxychlori-
nation unit. They base their estimate on the experience
they are now having with an incinerator designed to
handle liquid chlorocarbons. Their proposed system
includes an incinerator x^ith support fuel burners, a
flue gas quenching system and a flue gas scrubbing
system for removal of HC1.
-------
VCM-33
Table VC-6 presents a material balance for thermal
incineration and effluent scrubbing of the pseudo
typical oxychlorination vent stream (Table VC-4). In
order to have essentially complete combustion of pollu-
tants, the incineration is based on an l800°F combustion
zone temperature (0.5 sec. residence time) and 4 mol% (dry basis)
oxygen in the effluent. In order to obtain the l800°F
operating temperature,approximately 14 MM BTU/hr. of
supplemental fuel is required. Combustion of the
oxychlorination vent stream supplies about two-thirds
of the required heat. If the actual combustible content
of this stream is half of the value assumed, supplemental
fuel requirement would be double the value shown.
Since none of the surveyed plants use fired boilers or
any other combustion device on this vent stream, it is
difficult to predict equipment performance in this
application. Based upon applications in other areas,
the following potential problems exist:
1) Vent gas is normally available at low pressure.
2) Investment for required blowers, burning
equipment and control systems is high.
3) Effluent stream is corrosive at some conditions.
4) Flame control is difficult ana flame-outs can
be common due to low heating value arid low
level of incandescence.
5) Operating problem results from need to switch
to complete fuel gas firing whenever plant
emergency necessitates purging the reactor
system with nitrogen. This occurs about twice
a year.
The incinerator effluent is quenched and sent to either
a caustic scrubber or combination water-dilute caustic
scrubbing unit. The combination unit would be employed
if dilute HC1 (2-3 wt.% HC1) could be used off-site for
stream neutralization or sent to an HC1 recovery unit.
In the dual scrubbing unit, the gas stream is first
contacted with water, which absorbs about 90 percent of
the HC1. The gas is then scrubbed with caustic before
being discharged to the atmosphere. It is estimated that
the stack gases would contain less than one PPM of HC1 and
10 PPM by volume of chlorine„
Because of the corrosive properties of the incinerator
effluent at low temperature (<450°F), the bottom portion
of the scrubbing tower and inlet piping would be lined
-------
TABLE VC-6
THERMAL INCINETATOR AND SCRUBBER SYSTEN! FOR
530 MM LBS.AR. OXYCHLORTNATION PROCESS VENT GAS STREAM
Co-.sonent
C?.rton Eioxlde
Carbon Monoxide
! iror.cn
'.h-;ne
Ithylene
."'th-ne
r.thylene Mchlorlde
ilhyl Chloride
Vinyl Chloride
'/•\tcr
:':ji roc'rsloric Acid
Ch: or \n•?
"itrDsen Oxides
Kociu-r! hydroxide
Gcdiu-. Chloride
Total Lbs./'Hr.
SCF'M
Process
Vent Gas
'X
52,706
2,952
130
*35
454
386
101
59,531
13,085
i8oo°f
Flue Te.-np.
Process Vent Gas
100°F
Coir.bustlo.n Air
80° F
Natural Gas
i8oo°f
Combustion
Air
26,752
8,126
460
35,338
Quench
Water
/ \
Natural
Gas
54
527
120
701
Incinerator
Flue Gis
7,784
79,512
3,971
3,680
11
3
Quench
Water Caustic
Scrubber
Reject
95,570
21,230
56,795
56,795
Packed Tower
678
678
Flue Gas
175° F
Caustic Feed
19,03'+
991
<:U,00
Scrubber
Effluent
7,784
79,512
3,973
^1,7^5
1
3
133,018
34,690
Reject
175° F
-------
VCM-3 5
with fiber reinforced plastics (FRP) or rubber.
Porcelain raschig rings, Berl saddles or other types
of packing can be used.
Scrubber requirements for processing incinerator
effluent from the typical 530 MM lbs./yr. oxychlorina-
tion unit are as follows:
Combination Caustic
Unit Scrubber
Tower Dimensions, Ft.
Diameter 11 11
T-T Length 35 25
Water Absorption Section
Number of Beds 2
Bed Depth, Ft. (each) 8
Reject Water Rate, GPM 2 3
Wash Water Recirculation Rate, GPM 177
Bed A P, Inches of Water 2
Caustic Scrubbing Section
Number of Beds 1 2
Bed Depth, Ft. (each) 5 8
Spent Caustic Solution*, GPM 4 40
Caustic Recirculation Rate, GPM 151 155
Bed AP, Inches of Water 1 2
* Contains 5.0 weight percent NaCl.
The data presented in Table VC-6 are based on using
straight caustic scrubbing without HC1 recovery.
Based on published data ^ ^ and quotations from incin-
erator vendors,(8) it is estimated that the approximate
cost as of January 1975 for this emission control system
would be as follows:
Purchased Cost
Incinerator
Scrubber* *
Total
Installation Cost
Total
$110,000
215,000
325,000
490,000
$815,000
The above total investment for incinerating the oxychlori-
nation vent of a 700 MM lbs./yr. VCM is about one-third
the cost projected based on figures provided by
plant VC-6. It is difficult to determine installation
** Based on cost data provided by a licenser of
oxychlorination process.
-------
VCM-36
charges for installing new equipment in existing plants.
In addition the present high rate of inflation makes it
difficult to determine equipment costs. However neither
of these reasons appear adequate to explain the wide
variation in projected capital costs.
In addition to supplemental fuel this emission control
device will require 25 KWH/hr. electric power^ 115 GPM
process water and 65O-7OO lbs./hr. of caustic.
Most companies considering incinerators, and companies
selling this equipment, assume 100$! conversion of VCM to
HC1, H20, and CO2 is achieved. This assumption may be
far from true and performance tests on incineration
equipment should be made to determine actual conversion.
It is likely that such tests would show a wice variation
in VCM combustion efficiency since the operating tempera-
ture level and retention time used in the design of this
equipment appear to vary markedly.
VMD-8 - Direct Fired Boiler and Scrubber System
A direct fired boiler is another method of oxidizing the
oxychlorination process vent.
A large amount of steam is produced in the reactor system
of a conventional oxychlorination plant. Even with this
production, the overall facility (including direct
chlorination and VCM production) usually consumes a
substantial quantity of steam (about 2 lbs./lb. of VCM
production)„ Therefore^ in new plants, it is conceivable
that steam production resulting from pollution control
facilities could be used in the VCM complex.
Table VC-7 presents a typical material balance for a fired
boiler and scrubber system operating on the clean-up of
the oxychlorination vent gas. Incinerator data are based
on the same combustion zone operating conditions used for
the thermal incinerator. Maximum steam generation is
included in order to reduce cost and water requirements
for downstream scrubbing facilities.
Scrubbing data in Table VC-7 and subsequent economics
regarding vent gas incineration effluent scrubbing
operations are based on using a caustic scrubber similar
to that proposed for the thermal incinerator.
Burning of off-gas in a direct fired boiler results in
similar burning problems and combustion efficiency
anticipated for a thermal incinerator.
-------
TABLE VC-7
DIRECT FIRED BOILER PLUS SCRUBBER EMISSION CONTROL SYSTEM FOR
530 MM LBS./YR. OXYCHLORI NATION PROCESS VENT GAS STREAM
Component
Carbon Dioxide
Carbon Monoxide
Nitrogen
O.rytn
Vc thane
ethylene
r"ttv:-.e
ethylene Dichlorlde
I-.thyl Chloride
Vinyl Chloride
Yt ?ter
Hydrochloric Acid
Chlorine
:;itro--en Oxides
Sodium Hydroxide
Sodium Chloride
Total Lbs./Hr.
5CFM
Process
Vent Gas
1,598
441
52,706
2,962
130
318
^35
454
386
101
Combustion
Air
26,752
8,126
Natural
Gas
54
527
120
460
Incinerator
Flue Gas
7,784
79,511
3,971
3,680
609
11
it
Quench
Water
Caustic
Feed
59,531
13,085
35,338
701
95,570
21,230
27,524
27,524
Quench
Water
Scrubber
Reject
19,03^
678
678 .20,025
991
Flue Gas
140°F
550°F
Flue Temp
Packed Tower
Caustic Feed
Feed Water 35,500 Lbs./Hr. (240°F)
—«. Steam at 245 PSIG (Sat.)
33,800 Lbs./Hr.
80°F Corr.b. Air
:0°F
Natural Gas
Process Vent
Gas (100'Fr
Blowdown 1,700 Lbs./Hr. (404°F)
Scrubber
Effluent
7,784
79,511
3,973
12,474
1
4
103,7^7
24,210
<
12
Boiler
-------
VCM-38
In similar applications of fired boilers, it has been
found that the effluent stream is especially corrosive
at temperatures either above 600°F, or below the HC1 dew
point. In order to maintain steam coils within the non-
corrosive temperature range, 245 PSIG saturated steam is
assumed to be generated in the boiler and effluent gases
are exhausted at 550°F. Adequate instrumentation is
required to see that tube wall temperatures do not exceed
600°F or go below 400°F while burning streams containing
chlorinated hydrocarbons. Instrumentation is also
required for purging chlorinated compounds from the
system prior to furnace shutdown.
Based on data provided in a previous study of air pollution
control in EDC manufacture(^0, it is estimated that the
approximate investment for this control system (January
1975) would be as follows:
Purchased Cost
Direct Fired
Scrubber
Total
Installation Cost
Total
$ 490,000
160,000
$ 670,000
$1,000,000
$1,670,000
Supplemental fuel requirements are the same as for the
thermal incinerator. Estims.ted utility and chemical
requirements are as follows:
Electric Power - 100 KWH/Hr.
Process Water - 55 GPM
Boiler Feed Water - 71 GPM
Caustic - 650-700 Lbs./Hr.
As noted in Table VC-7, the facility would produce
33,800 lbs.Air. of steam (245 PSIG).
VMD-9 - Incineration Plus Steam Generation and
Scrubbing System
Table VC-8 presents a material balance and sketch for
a thermal incinerator followed by a waste heat boiler and
caustic scrubber. This combination facility has an
emissions control efficiency and potential similar to that
of the direct fired boiler. The effluent scrubber for
this unit would be the same as employed on the direct
fired boiler effluent.
There is very little commercial experience of burning
chlorinated hydrocarbons in incinerators with steam
generation for heat recovery. A Shell Chemical Company
-------
TABLE VC-8
THERMAL INCINERATOR PLUS STEAM GENERATION AND SCRUBBER SYSTEM
FOR
530 MM LB./YR. OXYCHLORINATION PLANT
PROCESS VENT GAS STREAM
MATERIAL BALANCE
Same as shown in Table vc-7
Flov Diagram
Flue Gas
140 °F
Quench
Water
550 °F
Flue Temp.
Packed Tower
Caustic Feed
Slowdown, 404 °F
1,700 lis./Hr.
Process Vent
Gas (100 °F)
Natural Gas
Combustion
Air (80 °F
1800
Boiler Feed
Water (240 °F)
35,500 lb8./hr.
¦Steam (? 245 PSIG, 750 °F
33,800 lbs./hr.
Reject
140 °F
-------
VCM-40
affiliate is reported to have had two 100 percent capacity
incinerator and boiler systems processing liquid chlori-
nated wastes in Europe. On-stream factor is believed to
have been approximately 25 percent because of brick work
deterioration and corrosion problems. This poor performance
has resulted in the project being abandoned.
Stauffer Chemical Company has a small fired tube boiler
in Bucks, Alabama which burns gaseous chlorinated waste
material.(9) This unit, built by John Zink Company, was
put in service in August of 1972. After six months
operation, it was shut down to replace corroded boiler
tubes and tube sheet (carbon steel) . Corrosion wa.s
attributed to a supplemental feed which contained
phosphorous. After retubing one-third of the bundle
(carbon steel tubes) and removing phosphorous containing
feed, the unit ran for two months before a shutdown was
caused by an expansion joint failure between the oxidizer
and boiler. The expansion joint had not been packed or
insulated and corrosion resulted from condensation during
cold weather. Boiler inspection during this shutdown
showed no corrosion. Since returning to operation, the
unit has run several months with no apparent corrosion
problems.
John Zink Company has a pilot unit similar in size to
the Stauffer facility.
American Chemical Corporation in Long Beach, California
has a thermal oxidizer plus waste heat boiler system for
disposal of concentrated gaseous chlorinated hydrocarbons.
American Chemical is on its third boiler. The first
boiler was water tube and failed within two years. The
second was fired tube and lasted five years. The present
boiler has been in service two years.
There are reports that there is a B.F. Goodrich licensee, AKZO
in HollanrJthat employs a thermal incinerator plus a
carbon steel boiler for heat recovery. This unit has been
in operation for two years and is reported to have given
satisfactory performance.
It is estimated that the approximate investment for this
type of control system (January 1975) would be as follows:
Purchased Cost
Incinerator
Waste Heat Boiler
Scrubber
Total
$ 110,000
165,000
180,000
455,000
685,000
Installation Cost
Total
$1,140,000
-------
VCM-41
Utility and chemical requirements for this facility-
would be the same as for the direct fired boiler system.
VKD-10 - Submerged Thermal Incineration and HC1 Recovery
Submerged exhaust incinerators are primarily used in
disposal of waste streams that have a high heating value.
The main advantage of this incinerator is that effluent
gas can be cooled to acceptable scrubber operating
temperature and reject a major portion of the HC1 as
dilute acid (2-5 wt.$ HC1) at relatively low capital
expense. However, when dealing with low heating value
waste streams such as the process vent gas, a substantial
amount of supplemental fuel is required to obtain
adequate combustion zone temperature (l800°F). While
combustion efficiency for this furnace would be similar
to other incinerator systems, overall heat utilization
is poor and operating costs would be higher than for the
above devices with steam generation.
VMD-11 - Catalytic Incinerator
A conventional catalytic incinerator could reduce pollutants
to similar levels obtained with a thermal unit. The catalytic
facility would operate at lower temperature (800-1000°F) thereby
reducing fuel consumption. However, the application of a
catalytic incinerator may have the following problems:
1) Only moderate catalyst life with possible
danger of catalyst fouling and poisoning.
2) Limited oxidation activity.
3) Based on thermodynamic equilibrium data,
low operating temperatures would favor
increased chlorine production. Chlorine
is more difficult to remove than HC1 in
downstream scrubbing facilities.
VMD-12 - Flare System
This control device would have the following limitations:
1) A substantial amount of supplemental fuel is
required to burn this vent stream. Based on
recommendations from vendors, about 125 BTU/SCF
is the minimum flareable heating value. This
would require about 75 MM BTU/hr. of supple-
mental fuel.
2) All HC1 formed during combustion (about 0.008
lbs./lb. of VCM product) would be emitted to
the atmosphere.
-------
VCM-42
3) Efficiency for removing contaminants is less
than for other combustion devices. Based upon
qualitative data from similar control devices
in other applications, it is estimated that
approximately 90 percent of the combustibles
would be burned.
4) Improper firing of the burner could result in
operating temperatures which favor N0X formation.
5) Changes in vent gas composition could extinguish
the burner if adequate instrumentation are not
provided.
VMD-13 - Contact Condenser
One plant (VC-5) passes the oxychlorination vent gas
through a direct contact condenser to recover EEC
(0,015 lbs./lb. VCM product) anc other light chlorinated
hydrocarbons (0.0015 lbs./lb. VCK). The process vent gas
is fed to the tube side of two shell and tube heat
exchangers operated in series. In the first exchanger
the gas is contacted with an unnamed absorption fluid and
indirectly cooled with processed vent gas. In the second
exchanger, refrigerant is used to further cool the
mixture. Liquid chlorinated hydrocarbons plus absorption
fluid are removed from the exchanger effluent in a vapor-
liquid separator. A decanting drum is used to separate
recovered hydrocarbons from the absorption fluid. The
recovered material (90 wt EDO) is combined with
oxychlorination reactor effluent liquid for water washing
and product distillation. The circulating absorption
fluid stream is sent to a stripper tower for removal of
water. Maloperation of the stripper occasionally
results in water recycle and condenser freeze-up.
Since the very limited survey data presented by plant VC-5
did not indicate operating condition and the VCM content
of the contact condenser feed and effluent, it is not
possible to determine the efficiency of this device for
reducing VCM emissions.
VMD-14 - Catalytic Reactor
One plant, VC-4, is installing a catalytic reactor
to reduce the total hydrocarbons in the oxychlorination
vent. They claim the device will reduce this material by
78$. According to their analysis there is about 0.24$
VCM in this stream and about 1.12$ of total reactive
hydrocarbons (including VCM). The stream contains
approximately 4.0$ oxidizing materials (oxygen, chlorine
and hydrochloric acid)» There is no indication as to how
-------
vcm-43
efficient this device is for reducing VCM. There
are no conditions given for this reactor nor are any
energy requirements noted. A number of catalytic systems
are possible but their effectiveness on very dilute
streams must be determined experimentally. No economic
data were given by plant VC-4 for their catalytic system.
C. Direct Chlorination Process Vent (Source Area H]_)
Most plants employ condensers to recover EDC from this
stream before scrubbing the vapor stream and venting the
non-condensibles to the atmosphere. Information regarding
the VCM content of the vent stream is not available. If
VCM is present, this relatively small stream can be sent
to the emission control device provided for the Dechlori-
nation process vent.
D. Loading and Storage Vents (Source Area C)
VMD-15 - Refrigeration
Two plants (VC-3 and VC-9) use low temperature refrigera-
tion to recover some VCM and reduce emission to the
atmosphere from product storage tanks and loading areas.
One, VC-3, maintains -10°F on the outlet vents from these
areas. The non-condensibles are sent to a flare. They
plan to add another refrigeration unit on the vent from
the light ends storage. Each unit represents 10 tons of
refrigeration and costs about $100,000 with an annual
operating cost of $27,000. The unit for the loading
area recovers between 5 to 10 thousand dollars per year
of VCM (equivalent to 0.0001 lbs./lb. of VCM product).
The new unit on the light ends will recover about $4,000
per year of VCM.
There are no data concerning the refrigeration unit used
by VC-9 other than they maintain 35 PSIG pressure on the
vent from their vent reactor. The temperature of the
vent is kept below 40°F and they recover about 85$ of
the VCM before the stream is vented to the atmosphere.
No cost figures are given by the manufacturer.
VMD-l6 - Tank Car And Dock Equalization System
Loading losses of VCM to tank cars or barges is one of the
largest sources of VCM emissions at VCM manufacturing
plants even though it is an intermittent source. One
plant, VC-2, uses an equalization system which equalizes
the pressure of the VCM storage tanks with the tank car
and barge. Then all VCM vapors from this equalized system
are fed back to the EDC absorber and completely recovered.
-------
VCM-44
Actually at the time their report was submitted (Fall of
1974) only the tank car loading facility was equalized
but early 1975 "they expect the dock facility also to be
operative. No cost figures are given, but since the
system is primarily piping, the cost is directly dependent
upon the distance the loading facilities are from the
absorber.
E. Fugitive and Miscellaneous Sources
VMD-17 - Sampling Systems
Most companies are presently taking precautions during
sampling that were not considered necessary Just over a
year ago. Two plants (VC-1 and VC-2) use what they call
a continuous loop sampler in which side streams of the
main process streams are continuously circulated anc can
be run through a sampling bomb to purge it completely
and then remove the bomb with negligible losses. We
have no cost figures for this system but believe it to
be under $50,000 f°^ all sampling points. Another plant,
VC-3j uses what they call a sealed system. It is somewhat
similar to the continuous loop sampler in as much as the
sample bomb (cylinder in this case) is purged by the
system back to the system but there is no continuous
sampling stream. They estimate that it would cost about
$25,000 to retrofit their sampling procedure to the
continuous system.
VMD-18 - Canned Pumps
There are a considerable number (10-20) high volume VCM pumps
required in the average size (700 million lbs./yr.,) VCM
plant and pump seals are probably the most persistent
source of fugitive VCM emissions. The use of canned pumps
would eliminate this problem and for a new plant should
not increase costs significantly if at all. To replace
the VCM pumps now in use at a current VCM plant would cost
about $10,000 per pump.
VMD-19 ~ Monitoring VCM Losses
In order to detect and eliminate leaks as soon as they
occur, it is necessary to continuously monitor specific
areas for VCM vapors. In a 700 million pounds per year
VCM plant probably five ten-point monitors are required
to provide adequate coverage. These instruments
(chromatographs) cost about $20,000 each. The associated
alarm and signal system costs another $30,000, and a data
processing system to keep up with the monitors another
40,000 to $90,000. This brings the total cost to about
200,000. In addition, a man is required with a portable
VCM detector to follow up alarms as well as monitor
-------
vcm-45
particular areas. He oftentimes will require the
assistance of a pipefitter. The monitors (chromatograph)
will need fairly continuous servicing by a day time
instrument man.
The monitoring of battery limits and off-site VCM con-
centrations is certainly required initially by most, if
not all, plants after allowable limits have been set,
but no estimate of this cost is made because of widely
divergent conditions for each plant.
-------
VCM-4 6
VII. Model Plants
To reduce emission of VCM, we have considered two models.
In the Model I plant, total VCM emissions other than fugi-
tive would be reduced by about 55-60%. In the Model II
plant, the VCM emissions would be reduced about 90%. These
percentage reduction figures apply to an average plant.
Listed below are the emission control devices by catalog
number for Model Plant I and IT and their costs:
Control Device
Device No.
7 00 MM Lbs/Yr VCM Plant
Model I
Model II
Refrigeration VMD-4
V7aste Heat Boiler VMD-6
Incinerator & Water VMD-9
Heat Boiler
Compr. & Refrigeration VMD-15
Cont. Loop Sampler VMD-17
Canned Pumps VMD-18
Monitoring VCM Leaks VMD-19
200,000
300,000
1,140,000
200,000 200,000
50,000 50,000
200,000
200,000 2 0 0,000
$650,000 $2,090,000
VMD-4 and VMD-15 are refrigeration units to reduce VCM
emissions from fractionating columns and loading and
storage facilities. Both are definite sources of VCM
emissions.
VMD-6 and VMD-9 are waste heat boilers designed to utilize
the heating value of the waste gas streams and hopefully
to reduce hydrocarbon and chlorocarbon emissions to
negligible values ( > 98% combustion). They both include
scrubbers to reduce resultant hydrogen chloride and chlorine
emissions to low values. VMD-6 is used on fairly high
chlorocarbon content vent streams from fractionation
facilities. The incineration is presumably very efficient
(98+%) in reducing VCM emissions. VMD-9 is used to handle
the emissions from the oxychlorination unit which has a low
VCM and combustible content and is a large volume stream.
The efficiency of this incineration is unknown but should be
over 98%. The fuel requirement for this waste heat boiler
depends on the combustible content of the oxychlorination
vent stream. Presumably these two units (VMD-6 and VMD-9)
in the Model II plant could be combined into one single
waste heat boiler and scrubber at a substantial capital
cost savings, say $150,000, if the emission sources were
in reasonable proximity.
VMD-17 is a sampling system (primarily piping) so that
representative samples can be obtained with minimal material
loss and negligible exposure level to sampling personnel.
-------
VCM-47
VMD-18 represents the cost of changing to canned pumps in
order to eliminate packing or seal losses which are among
the major fugitive VCM losses.
VMD-19 represents the costs of putting in an adequate
monitoring system to detect VCM leaks or losses and reduce
or eliminate them before they become major emission sources.
Most, if not all, VCM plants now have such systems in
operation and they have been a major factor in reducing
the general level of VCM emissions throughout the industry.
The emission drop to be expected from the various devices
for the Model Plants is shown in Table VC-9.
The total emissions shown in Table VC-9 for a typical existing
plant without control devices of 0.005435 lbs./lb. product is
much higher than the average of 0.001825 shown for all plants
in Figure VC-5. This is true for two important reasons, one is
that most plants have some emission control devices operating,
the other is that most plants have not included emissions
from the oxychlorination unit(s) which can be very significant.
Model I plant indicates an overall reduction of 55%, allowing
for a 25% reduction of fugitive emissions by continuous and
careful monitoring. The reduction for the Model II plant is
90%.
The utility requirements of these emission control devices for
the Model plants is tabulated below:
Device No.
Model I
Mode1 II
VMD-4
Electricity
Cooling Water
VMD-6
Electricity
Process Water
Boiler Feed Water
Caustic
Fuel
Steam Generated (245 PSIG)
VMD-9
Electricity
Process Water
Boiler Feed Water
Caustic
Fuel
Steam Generated (245 PSIG)
VMD-15
Electricity
Cooling Water
VMD-17 & VMD-19
VMD-18
4 0 KWH/Hr
30 GPM
4 5 KWH/Hr
3 5 GPM
11 GPM
650 Lbs/Hr
2 MM BTU/Hr
5,000 Lbs/Hr
10 0 KWH/Hr
55 GPM
71 GPM
700 Lbs/Hr
14-28 MM BTU/Hr
33,800 Lbs/Hr
40 KWH/Hr 4 0 KWH/Hr
30 GPM 30 GPM
(No significant utility requirements.)
(No additional utility requirements
ever present pumps.)
-------
TABLE VC-9
VCM EMISSIONS FROM BALANCED ETHYLENE VCM MODEL PLANTS
Typical Existing Plant
No Control Devices
Source Area Lbs/Lb Prod Cont. Dev. No. Lbs/Lb Prod
Model Plant I
Model Plant II
Eff Cont. Dev. No. Lbs/Lb Prod
Eff
7a
A & Ai
C
D
F
G
Hi & H2
Fugitive
000500
002400
000796
000038
000003
000078
001320
000300
VMD-4
VMD-4
VMD-15
VMD-17
(1)
VMD-19
(2)
000100
000600
000119
000009
000003
000078
001320
000225
80%
75%
85%
75%
VMD-4
VMD-6
VMD-15
VMD-17
VMD-9
(1)
25%
(3) (2)
VMD-18 & 19
.000100
. 000048
.000119
. 000009
.000003
. 000078
.000026
. 000150
80%
98%
85%
75%
98%
50%
Total
005435
.002454
55%
. 000533
90%
Notes:
(1) One plant reduced sampling losses by 75% using a continuous loop sampler.
(2) Fugitive emissions reduced 25% by careful monitoring and good housekeeping.
(3) Fugitive emissions further reduced by use of canned pumps. The 50% reduction is
strictly an assumption, there is no satisfactory data to indicate maximum possible reduction.
-------
VCM-49
Table VC-10 shows the manufacturing costs for a typical
existing VCM plant of 700 MM lbs./year productivity without
any omission control devices. Table VC-11 shows costs for
our Model I and II plants incorporating the emission control
devices noted in Table VC-9. Table VC-12 is a Pro Forma
Balance sheet for the three plants and indicates the
increased capital investment required as more emission
devices are employed.
-------
VCM-50
TABLE VC-10
VINYL CHLORIDE MANUFACTURING COST FOR A
TYPICAL EXISTING 700 MM LBS./YEAR PLANT
JANUARY 197 5
Direct Manufacturing Cost
Raw Material
Ethylene @ 8^/lb.
Chlorine @ 6-1/4^/lb.
Catalyst and Chemicals
Labor @ 5 Men/Shift @ $5.65/hr.
Maintenance @ 5$ of Investment
Utilities
^/Lb .
3.73
3-67
0.02
0.04
0.17
0.50
8.13
$/Y r.
Indirect Manufacturing Cost
Plant Overhead (110$ Labor)
Laboratory (25$ Labor)
0.05
0.01
0.06
Fixed Manufacturing Cost
Depreciation (10-yr. Straight Line)
Insurance & Property Tax (2.3$ Investment)
Manufacturing Cost
0.35
0.08
0.43
8.62
General Expenses
Administration (3$ of Manufacturing Cost)
Sales (1$ of Manufacturing Cost)
Research (2,5$ of Manufacturing Cost)
Finance (b$ of Investment)
0.26
0.09
0.2i
0.21
0.77
Total Cost
Product Value
Profit Before Taxes
Profit After 52$ Taxes
ROI (NPAT X 100/Plant Investment)
9.39
10.50
1.11
0.53
15.4$
65,730,000
73,500,000
7,770,000
3,730,000
-------
VCM-51
TABLE VC-11
VINYL CHLORIDE MANUFACTURING COST FOR
700 MM LBS./YR. PLANTS WITH CONTROL DEVICES
JANUARY 1975
Model I
g!/Lb.
Model II
4/Vz.
$Ar.
Direct Manufacturing Cost
Raw Materials
Ethylene
Chlorine
Catalyst & Chemicals
Labor @ $5.65/Hr.
Maintenance @ 5$ Investment
Utilities
3.73
3.67
0.02
0.04 (6 Men/Shift)
0.18
0.50
8.14
3.73
3.67
0.14
0.05 (7 Men/Shift)
0.19
0.45
8.23
Indirect Manufacturing Cost
Plant Overhead (110$ Labor)
Laboratory (25$ Labor)
0.05
o.oi
0.06
0.06
0.01
0.07
Fixed Manufacturing Cost
Depreciation (10 yr. st. line)
Insurance & Property Tax
(2.3$ Investment)
Manufacturing Cost
General Expenses
Administration (3$ Mfg. Cost)
Sales (1% of Mfg. Cost)
Research (2.5$ of Mfg. Cost)
Finance (6$ Investment)
Total Cost
Product Value
Profit Before Taxes
Profit After Taxes
R0I (NPAT X 100/plant Invest.)
0.35
0.08
0I3
8.63
0.26
0.09
0.21
0.21
0.77
10.50
1.10
0.53
14.8$
0.38
0.09
oTW
8.77
0.26
0.09
0.22
0.23
0.80
9.40 65,800,000 9.57 66,990,000
73,500,000
7,700,000
3,696,000
10.50 73,500,000
0.93 6,510,000
0.495 3,125,000
11.956
-------
TABLE VC-12
PRO-FORMA BALANCE SHEET
700 MM LBS./YR. VCM PLANT - BALANCED ETHYLENE PROCESS
JANUARY 1975
Type of Unit
Current Assets
Cash (1)
Accounts Receivable (2)
Inventories (3)
Fixed Assets
Plant
Building
Land
Total Assets
Current Liabilities (4)
Equity & Long-Term Dept.
Total Capital
Existing
$ 5,028,300
6,125,000
6,573,000
23,900,000
250,000
100,000
$41,976,300
$ 5,104,200
36,872,100
$41,976,300
Improved Existing
Model I
$ 5,034,200
6,125,000
6,580,000
24,550,000
250,000
100,000
$42,639,200
$ 5,110,000
37,529,200
$42,639,200
Model II
$ 5,115,800
6,125,000
6,699,000
25,990,000
250,000
100,000
$44,279,800
$ 5,17^,200
39,105,600
$44,279,800
Notes:
(1) Based on one month's total manufacturing cost.
(2) Based on one month's sales.
(3) Based on 10$ of annual production at cost.
(4) Based on one month's total cost less fixed manufacturing and finance costs.
-------
VCM-5 3
VIII. Research and Development Goals
As with PVC plants, the obvious goals are to reduce VCM
emissions significantly. However, unlike PVC plants, the
emissions from VCM plants are considerably less on a
pound per pound basis but considering the large size of
most VCM plants, their actual total pounds of emission
can be large in a given area.
One of the major sources of VCM emissions is the vent from
the oxychlorinatjon unit in the balanced ethylene process.
This was not noted in our report on "Ethylene Dichloride
by Oxychlorination"^) At the time of that report, there
was no special concern about VCM. Nov; tests are made to
parts, per million and it is found that VCM is present .in
this vent stream, usually several hundred parts per
million. The oxychlorination vent stream is a large
stream containing small percentage of combustible (<3.0
vol.%). Incinerators, waste heat boilers, etc. are all
possible control devices but the first consideration
should be to determine how complete the combustion of
VCM is under various reasonable conditions of temperature,
residence time, and other factors that could effect
reaction rates and equilibrium. From data given by plant
VC--3, they indicate something under 99% completion and
it could be considerably less on very dilute streams.
The possibility of carbon adsorption techniques can only
be confirmed by an "in-depth'1 study of carbon adsorption
isotherms on a wide range of chlorocarbons in the
presence of water vapor. One of the most important
considerations of the many parameters to be studied is
the life of the activated charcoal and if there are any
"poisoning" ingredients present,,
As all the processes involved, direct chlorination
(hydrochlorination where acetylene is involved), oxy-
chlorination and pyrolysis of EDC are all continuous, there
is not much than can be done procedurally to reduce VCM
emissions other than close monitoring and good
"housekeeping".
One of the two plants using the direct hydrochlorination
of acetylene has installed what they term a "vent reactor"
on the vent from their main reactor. However, the vent
from this "vent reactor" which is cooled to below 40°F
(4.4°C) at 35 PS1G emits more VCM than any other single
source (on a pound per pound of product basis) of all the
VCM plants surveyed. As this process is probably obsolete
and the actual production low (far below nameplate capacity),
-------
vcm-54
this particular source of VCM emission may be non-
existent in the near future. We would not recommend
any research or development program for reducing this
emission unless the process should be revived and the
plant operated at or near capacity.
-------
VCM- 55
REFERENCES
1. Albright, L. F», "Fi-oeeases for Major Addition - Type Plastics
and Their Monomers", McGraw Hill, Inc., New York, N.Y., 197^ •
2. U.S. Tarriff Commission Report, March 6, 197^•
3. "Survey Reports on Atmospheric Emissions from the Petrochemical
Industry, Vol. Il", U.S. Environmental Protection Agency
Report EPA-450/3-73-005-b, April 1972*-.
4. "Engineering and Cost Study of Air Pollution Control for the
Petrochemical Industry, Vol. 3- Ethylene Bichloride
Manufacture by Oxychlorination", U.S. Environmental
Protection Agency Report 1PA-45O/3-73-O06-C.» November 1974.
5. "Chemical Economics Handbook", Stanford Research Institute,
September 1973.
6. "Controlling Vinyl Chloride Emissions with Granular Activated
Carbon", Bulletin 23-200, Calgon Corporation, Pittsburgh,
Pennsylvania, 197^-.
7. Rolke, R. W., et al, "Afterburner Systems Study", by Shell
Development Company for Environmental Protection Agency
(Contract EHS-D-71-3)•
8. Private Communications with Reeco Regenerative Environmental
Equipment Company, Inc., Palisades Park, New Jersey.
9. Herrington, L. E., "Ethyl Chloride Gas Stream Consumed by
Thermal Oxidation", Chemical Processing! page 20, September
1973.
-------
APPENDIX I
BASIS OF THE STUDY
I. Industry Survey
The study which led to this document was undertaken to obtain information
about selected production processes that are practiced in the Petrochemical
Industry. The objective of the study was to provide data for the EPA to use
in the fulfillment of their obligations under the Clean Air Amendments of 1970.
The information obtained during the study includes industry descriptions,
air emission control problems, sources of air emissions, statistics on quantitie
and types of emissions and descriptions of emission control devices currently
in use. The principal source for these data was an Industry Questionnaire
but it was supplemented by plant visits, literature searches, in-house back-
ground knowledge and direct support from the Manufacturing Chemists Association.
More than 200 petrochemicals are currently produced in the United States,
and many of these by two or more different processes. It was obvious that
the most immediate need wa6 to study the largest tonnage, fastest growth
processes that produce the most pollution. Consequently, the following 32
chemicals (as produced by a total of 41 different processes) were selected
for study;
Acetaldehyde (two processes)
Acetic Acid (three processes)
Acetic Anhydride
Acrylonitrile
Adipic Acid
Adiponitrile (two processes)
Carbon Black
Carbon Disulfide
Cyclohexanone
Ethylene
Ethylene Dichloride (two processes)
Ethylene Oxide (two processes)
Formaldehyde (two processes)
Glycerol
Hydrogen Cyanide
Maleic Anhydride
Nylon 6
Nylon 6,6
"Oxo" Alcohols and Aldehydes
Phenol
Phthalic Anhydride (two processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Terephthalic Acid (1)
Toluene Di-isocyanate (2)
Vinyl Acetate (two processes)
Vinyl Chloride
(1) Includes dimethyl terephthalate.
(2) Includes methylenediphenyl and polymethylene polyphenyl isocyanates.
The Industry Questionnaire, which was used as the main source of information
was the result of cooperative efforts between the EPA, Air Products and the
EPA's Industry Advisory Committee, After receiving approval from the Office of
Management and Budget, the questionnaire was sent to selected producers of
most of the chemicals listed above. The data obtained from the returned
questionnaires formed the basis for what have been named "Survey Reports".
These have been separately published in four volumes, numbered EPA-450/3-73-005a
b, c, and d and entitled "Survey Reports on Atmospheric Emissions from the
Petrochemical Industry - Volumes I, II, III, and IV.
-------
1-2
The purpose of the survey reports was to screen the various petrochemical
processes into the "more" and "less - significantly polluting processes".
Obviously, significance of pollution is a term which is difficult if not
impossible to define because value judgements are involved. Recognizing this
difficulty, a quantitative method for Significant Emission Index (SEI) was
developed. This procedure is discussed and illustrated in Appendix II of
this report. Each survey report includes the calculation of an SEI for the
petrochemical that is the subject of the report. These SET.'s have been
incorporated into the Emission Summary Table that constitutes part of this
Appendix (Table I). This table can be used as an aid when establishing
priorities in the work required to set standards for emission controls on
new stationary sources of air pollution in accordance with the terms of the
Clean Air Amendments of 1970.
The completed survey reports constitute a preliminary data bank on each
of the processes studied. In addition to tha SEI calculation, each report
includes a general introductory discussion of the process, a process description
(including chemical reactions), a simplified process flow diagram, as well as
heat and material balances. More pertinent to the air pollution study, each
report lists and discusses the sources of air emissions (including odors and
fugitive emissions) and the types of air pollution control equipment employed.
In tabular form, each reports summarizes the emission data (amount, composition,
temperature, and frequency); the sampling and analytical techniques; stack
numbers and dimensions; and emission control device data (types, sizes, capital
and operating costs, and efficiencies).
Calculation of efficiency on a pollution control device is not necessarily
a simple and straight-forward procedure. Consequently, two rating techniques
were developed for each type of device, as follows:
1. For flares, incinerators, and boilers a Completeness of Combustion Rating
(CCR) and Significance of Emission Reduction Rating (SERR) were used.
2. For scrubbers and dust removal equipment, a Specific Pollutant
Efficiency (SE) and a SERR were used.
The bases for these ratings and example calculations are included in
Appendix III of this report.
II. In-Depth Studies
The original performance concept was to select a number of petrochemical
processes as "significant polluters", on the basis of data contained in
completed questionnaires. These processes were then to be studied "in-depth".
However, the overall time schedule was such that the EPA requested an initial
selection of three processes on the basis that they would probably turn out
to be "significant polluters". The processes selected in this manner were:
1. The Furnace Process for producing Carbon Black.
2. The Sohio Process for producing Acrylonitrile.
3. The Oxychlorination Process for producing 1,2 Dichloroethane
(Ethylene Dichloride) from Ethylene.
-------
TAB If I
EMISSIONS SUMMARY
Page 1 of 3
ESTIMATED W CURRENT AIR EMISSIONS. HH LBS./YEAR
Hydrocarbons
Particulates
Oxides of NitroRen
Sulfur Oxides
Carbon Monoxide
Total
Total Vein
Acatildehyda via Ethylene
1.1
0
0
0
0
1.1
86
via Ethanol
0
0
0
0
27
27
27
Acetic Acid via Methanol
0
0
0.01
0
0
0.01
1
via Butane
AO
0
0.04
0
14
54
3,215
via Acetaldehyde
6.1
0
0
0
1.3
7.4
490
Acetic Anhydride via Acetic Acid
3.1
0
0
0
5.5
8.6
253
Aeryloaltrlie (9)
183
0
5.5
0
196
385
15,000
Adlplc Acid
0
0.2
29.6
0
0.14
30
1,190
Adlp>nltrlle via Butadiene
11.2
4.7
50.5
0
0
66.4
3,200
via Adlplc Acid
0
0.5
0.04
0
0
0.54
30
Carbm Black
156
8.1
6.9
21.6
3,870
4,060
17,544
Carbjq Disulfide
0.15
0.3
0.!
4.5
0
5.1
120
Cycl)hexiaon«
70
0
0
0
77.5
148
5,700
Dloic:hyl Terephthalate (+TPA)
91
1.4
0.1
1,0
53
146.5
7 ,4b0
Ethy;ene
15
0.2
0.2
2.0
0.2
17.6
1.240
Ethylene Dlchlorlde via Oxychlorlnatlon
95.1
0.4
0
0
21.8
117.3
7,650
via Direct Chlorlnatlon
29
0
0
0
0
29
2,300
Ethy .ene Oxide
85.8
0
0.3
0.1
0
86.2
6,880
foiELildehyde via £llver Catalyat
23.8
0
0
0
107.2
131
1,955
via Iron Oxide Catalyat
25.7
0
0
0
24.9
50.6
2,070
Glycerol via EplchlorohydrIn
16
0
0
0
0
1 b
1,280
K^drngen Cyanide Direct Process
0.5
0
0.41
0
0
0.91
56
Isccyanates
1.3
0.8
0
0.02
86
88
231
Kale: c Anhydride
34
0
0
0
260
294
2,950
My 1 o 11 6
0
1.5
0
0
0
1.5
90
Nylon 6,6
0
5.5
0
0
0
5.5
330
Oxo ITocen
5.25
0.01
0.07
0
19.5
24.8
440
Phenol (
24.3
0
0
0
0
24.3
1 ,940
Phthi.llc Anhydride via O-Xylene
0.1
5.1
0.3
2.6
43.6
51.7
422
via Naphthalene
0
1.9
0
0
45
47
160
High Density Polyethylene
79
2.3
0
0
0
81.3
6,400
Lov penalty Polyethylene
75
1.4
0
0
0
76.4
6,100
Polyjropylene
37.5
0.1
0
0
0
37.6
2,950
Polyityrene
20
0.4
0
1.2
0
21.6
1,650
Polyvinyl Chloride
62
12
0
0
0
74
5,700
Styre tie
4.3
0.07
0.14
' 0
0
4.5
355
Styrene-Butadlene Rubber
9.4
1.6
0
0.9
0
12
870
Vinyl Acetate via Acetylene
5.3
0
0
0
0
5.3
425
via Ethylene
0
0
TR
0
0
TR
TR
Vinyl Chloride
17.6
0.6
_0
_0
0
18.2
1.4b0
Total*
1,227.6
49.1
94.2
33.9
4,852.6
6,225-9
110,220
(5)
(1) la most ioafeances numbers are based on lees than LOO*/, survey. All based on engineering judgement of beat current control.
(2) Assumes future plants will employ bent current control techniques.
(3) Exclude* methane, IncLudea H2S and all volatile organic®.
(4) Includes non-volatile organic* and inorganics.
(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, N0X - AO, S0X - 20,
-------
TA'ILE I
EMISSION SUMMARY
page 2 of 3
ESTIMATED ADDITIONAL (2)
AIR EMISSIONS IN
1980, MM LBS./YEAR
Hydrocarbons
Particulates
Oxides of Nitrogen
Sulfur Oxides
Carbon Monoxide
Total
Total Weighted
Acetaldehyde via Ethylene
1.2
0
0
0
0
1.2
96
via Ethanol
0
0
0
0
0
0
0
Acetic Acid via Methanol
0
0
0.04
0
0
0.04
2
via Butane
0
0
0
0
0
0
0
via Acetaldehyde
12.2
0
0
0
2.
,5
14.7
980
Acetic Anhydride via Acetic Acid
0.73
0
0
0
1.
.42
2.15
60
Aery Ion itrile (9)
284
0
8.5
0
304
596
23,000
Adipic Acid
0
0.14
19.3
0
0.
,09
19.5
779
Adiponitrile via Butadiene
10.5
4.4
47.5
0
0
62.4
3,010
via Adipic Acid
0
0.5
0.04
0
0
0.54
30
Carbon Black
64
3.3
2.8
8.9
1,590
1,670
7,200
Carbon Disulfide
0.04
0.07
0.03
1.1
0
1.24
30
Cyclohexanone
77.2
0
.0
0
85,
, 1
162
6,260
Dinethyl Tcrephthalate (+TPA)
73.8
1.1
0.07
0.84
42,
.9
118.7
6,040
Ethylene
14 o 8
0.2
0.2
61.5
0.
,2
77
2,430
Ethylene Dichloride via Oxychlorination
110
0.5
0
0
25
136
8,800
via Direct Chlorlnation
34.2
0
0
0
0
34.2
2,740
Ethylene Oxide
32.8
0
0.15
0.05
0
33
2,650
Formaldehyde via Silver Catalyst
14.8
0
0
0
66.
.7
81.5
1,250
via Iron Oxide Catalyst
17.6
0
0
0
17,
.0
34.6
1,445
Glycerol via Epichlorohydrin
8.9
0
0
0
0
8.9
700
Hydrogen Cyanide Direct Process
0
0
0
0
0
0
0
Isocyanates
1.2
0.7
0
0.02
85
87
225
Maleic Anhydride
31
0
0
0
241
272
2,720
Nylon 6
0
3.2
0
0
0
3.2
194
Ny 1 on 6,6
0
5.3
0
0
0
5.3
318
Oxo Process
3.86
0.01
0.05
0
14.
.3
18.2
325
Phenol
21.3
0
0
0
0
21.3
1,704
Phthalic Anhydride via O-Xylene
0.3
13.2
0.8
6.8
113
134
1,100
via Naphthalene
0
0
0
0
0
0
0
High Density Polyethylene
210
6.2
0
0
0
216
17,200
l.ow Density Polyethylene
2 6?
5
0
0
0
267
21 ,300
Po lypropy1enc
152
0.5
0
0
0
152.5
12,190
Polystyrene
20
0.34
0
1.13
0
21.47
1,640
Polyvi ny1 Chlor ide
53
10
0
0
0
63
4 ,840
Styrene
3.1
0.05
0.1
0
0
3.25
225
Styrene-Butadiene Rubber
1.85
0,31
0
0.18
0
2.34
170
Vinyl Acetate via Acetylene
4.5
0
0
0
0
4.5
360
via Ethylene
0
0
TR
0
0
TR
TR
Vinyl Chloride
26,3
0.9
0
_0
0
27.2
2,170
Totals
1,547.2
55,9
79P5
80.5
2,588
4,351.9
134,213 O)
(1) In most instances nurabcrs are based on less than 1007. survey. All based on engineering judgement of best current control. Probably has up to 107, lov bias.
(2) Assumes future plants will employ best current control techniques.
(3) Excludes methane, includes H2S and all volatile organics.
(4) Includes non-volatile organica and inorganics.
(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, NO* - 40, S0X - 40, and CO - 1.
(6) Referred to elsewhere in this jtudy as "Significant Emission Index" or "SEI".
(7) Totals are not equal across and dovn duv to rounding.
(9) See sheet I of 3.
-------
TABLE I
EMISSIONS SUMMARY
Page 3 of 3
Emissions
(2), MM Lbs./Year
Total Esttix
ited Capacity
Estimated Number of Nev Plants
MM
Lbs./Year
Total bv 1980
Total Weighted (5) hvr 1980
(1973 - 1980)
Current
Bv 1980
Acetaldehyde via Ethylene
2.3
182
6
1,160
2,4t>0
via Ethanol
27
27
0
96ft
9nt>
Acetic Acid via Methanol
0.05
3
U
400
1 .800
via Butane
54
3,215
0
1,020
500
via Acetaldehyde
22
1,4 70
3
875
2,015
Ace :1c Anhydride via Acetic Acid
10.8
313
3
1,705
2,100
Aerylonltrlle (9)
980
38,000
5
1,165
3,700 (8)
Adl|>lc Acid
50
1,970
7
1,430
2,200
Adlpoultrlle via Butadiene
128.8
6,210
4
435
845
via Adlplc Acid
1.1
60
3
280
550
Carl on Black
5,730
24,740
13
3,000
5,000 (8)
Carl'On Disulfide
6.3
150
2
871
1,100
Cyc]ohexanone
310
11,960
10
1,800
3 ,600
Dlnwthyl Terephthalate (+TPA)
265
13,500
8
2,865
5,900
Eth) lene
94
3,670
21
22,295
40,000
Eth)lene Dlchlorlde via Oxychlorlnetlon
253
16,450
8
4,450
8,250 (8)
via Direct Chlorlnatlon
63
5,040
10
5,593
11,540
Eth)lene Oxide
120
9,530
15
4,191
6,800 (8)
Fornaldehyde via Sliver Catalyst
212.5
3,205
40
5,914
9,000
via Iron Oxide Catalyst
85
3,515
12
1,729
3,520 (8)
Clycerol via Eplchlorohydrln
25
2,000
1
245
380
Hydrogen Cyanide Direct Process
0.5 (10)
28 (10)
0
412
202
Isocyanates
175
456
10
1,088
2,120
Malelc Anhydride
566
5,670
6
359
720
Nylon 6
4.7
284
10
486
1,500
Nylon 6,6
10.8
650
10
1,523
3,000
Oxo Process
43
765
6
1,727
3,000
Phenol
46
3,640
11
2,363
4,200
Phthillc Anhydride via O-Xylene
186
1,522
6
720
1,800 (8)
via Naphthalene
47
160
0
603
528
High Density Polyethylene
297
23,600
31
2,315
8,500
Lov Density Polyethylene
34 3
27,400
41
5,269
21,100
Poly iropy lene
190
15,140
32
1,160
5,800
Poly.ityrane
43
3,290
23
3,500
6,700
Polyvinyl Chloride
137
10,540
25
4,375
8,000
Styrcne
7.4
610
9
5,953
10.000
Styrune-Butadlene Rubber
14
1,040
4
4,464
5,230
Vlny . Acetate via Acetylene
9.8
785
1
206
356
via Ethylene
TR
TR
4
1,280
2,200
Vinyl. Chloride
45
3,630
10
5,400
13,000
Totals 10,605 244,420
(1) In most instance* number* are baaed on leas than 1007. survey. All based on engineering judgement of beat current control. Probably has up to 107v low bias.
(2) Assumes future plants will employ best current control techniques.
(3) Excludes methane, includes H2S and all volr.tlle organica.
(4) Includes non-volatile orgaoics and inorganics.
(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, N0X - 40, S0X - 20, and CO - 1.
(6) Referred to elsevhere in this atudy as "Slgnifleant Emission Index" or "SEI".
(7) Totals are not equal across aad dovn due to rounding.
(8) By 1985.
(9) See sheet 1 of 3
[10) Xie to anticipated future ahut dovn of marginal plants*
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1-6
In order to obtain data on these processes, the operators and/or
licensors of each were approached directly by Air Products' personnel.
This, of course, was a slow and tedious method of data collection because
mass mailing techniques could not be used, nor could the request for data
be identified as an "Official EPA Requirement". Yet, by the time that OMB
approval was given for use of the Industry Questionnaire, a substantial,
volume of data pertaining to each process had already been received. The
value of this procedure is indicated by the fact that first drafts of these
three reports had already been submitted to the EPA, and reviewed by the
Industry Advisory Committee, prior to the completion of many of the survey
reports.
In addition, because of timing requirements, the EPA decided that
four additional chemicals be "nominated" for in-depth study. These were
phthalic anhydride, formaldehyde, ethylene oxide and high density
polyethylene. Consequently, five additional in-depth studies were
undertaken, as follows:
1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.
2. Air Oxidation of Methanol in a Methanol Rich Process to
produce Formaldehyde over a Silver Catalyst. (Also, the
subject of a survey report.)
3. Air Oxidation of Methanol in a Methanol-Lean Process Lo
produce Formaldehyde over an Iron Oxide Catalyst.
4. Direct Oxidation of Ethylene to produce Ethylene Oxide.
5. Low pressure catalytic polymerization of Ethylene.
The primary data source for these was the Industry Questionnaire,
although SEI rankings had not been completed by the time the choices
were ir.ade.
In addition separate "In-Depth" studies were made on Polyvinyl
Chloride (PVC) and Vinyl Chloride Monomer (VCM) using data obtained
from a separate survey made in the summer of 1974.
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